Professional Documents
Culture Documents
12.1 Introduction
Stainless steels contain from 10 to 30% chromium. Varying amounts of nickel, molybdenum, copper, sulfur, titanium, niobium, etc. may be added to obtain desired mechanical properties and service life. Stainless steels are primarily classified as austenitic, ferritic, martensitic, duplex or
precipitation hardening grades. The first stainless steel grades that were commercially produced in
the United States were similar to 302, 410, 420, 430, and 446. These five alloys were produced
and marketed prior to 1930. In subsequent years, the grades similar to 303, 304, 316, 321, 347,
416, and 440 were brought to market.
In the early stages of their production, stainless steels were melted using an electric arc furnace.
Stainless steels were made to contain no more than 0.12% carbon. A large fraction of production
of stainless steels was melted to a maximum carbon content of 0.07 or 0.08%.
In those early days, carbon steel scrap, iron ore, and burnt lime were charged into an electric arc
furnace. After the scrap was molten, carbon was removed by adding ore until the carbon content
reached 0.02%. The electrodes were then raised and the slag removed as completely as possible.
Desired amounts of ferrosilicon, burnt lime, and fluorspar were added and the temperature of the
bath was raised so that a large amount of low carbon ferrochromium could be added to achieve the
aim chromium level. The desired amount of the low carbon ferrochromium was added in two or
three separate batches. The bath had to be mixed thoroughly by rabbling or reladling and slag had
to be kept fluid by continuous additions of ferrosilicon, lime and fluorspar. After all the desired
chromium was in the alloy, a sample was taken for preliminary analysis. Final additions were made
and the heat was brought to the desired tapping temperature and tapped.1
Until about 1970, the majority of stainless steel was produced in the arc furnace. With the advent
of tonnage oxygen production, the electric furnace stainless steel melting practice changed from
the above. Gaseous oxygen could be used to improve the rate of decarburization. This could be
achieved by injecting oxygen gas into the liquid steel using a water-cooled lance. The faster oxidation of carbon with high oxygen potential was accompanied by the adverse reaction of extensive
oxidation of chromium to the slag. This necessitated a well-defined reduction period in which ferrosilicon was used to reduce the oxidized chromium from the furnace slags.
In the late 1960s, a number of laboratory studies were performed to understand the thermochemistry of the stainless steels.2 One of these studies was by Krivsky, who studied the carbonchromium-temperature relationships. His experiments involved blowing oxygen onto the surface
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
715
of the baths of molten chromium alloys. He was trying to perform the experiments under isothermal conditions but found it difficult because of the exothermic nature of the oxidation reactions.
Krivsky added argon to oxygen in order to control the temperature. He found that with argon dilution he could decarburize the melt to even lower levels of carbon without excessive oxidation of
chromium.3
Krivskys observations led to initial experiments where argon-oxygen mixtures were injected
through a lance into the bath in the arc furnace. It was found that argon injection in the wide and
shallow bath of an arc furnace did not influence the decarburization reaction completely as predicted. Hence, after many experiments, the developers decided that a separate refining vessel was
necessary to develop a commercial process. At Joslyn Steel (now Slater Steels), a 15-ton converter
with three tuyeres was built. The first successful heat was made in October 1967. These successful trials led to patents for the argon-oxygen decarburization (AOD) process for the refining of
stainless steels and other specialty alloys4 by the industrial gases division (now Praxair, Inc.) of
the Union Carbide Corporation.
The AOD process revolutionized stainless steelmaking. It lowered the cost of production of
stainless steels significantly. It allowed operators to use electric arc furnaces for melting down of
1996
1983
AOD
71.8%
AOD
68.7%
4.2% EAF
6.8% VOD
9.2% VOD
5.0% Converter
4.4% Converter
19.5% Converter / VOD
Top lance
(O2, Ar, N2)
Gases
(Ar, O2, N2, air)
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Cooling scrap
Alloying material
Burnt lime
O2
Ar
Sublance
N2
Waste gas
Tuyereprocess gas
of the chromium and nickel as well as some other alloying elements, is the charge to the converters. The converters are used to achieve low carbon stainless steels which may be tapped into a
teeming ladle. The EAF-AOD process is one such duplex route. The versatility of the AOD process
led steelmakers to re-examine the use of different converters for melting of stainless steels. This
led to the development of several other converters for duplex processes. These include: KCB-S6
process developed by Krupp Stahl, shown in Fig. 12.3; K-BOP7 process used by Kawasaki Steel
Corporation; K-OBM-S8 promoted by Voest Alpine; metal refining process (MRP)9 developed by
Mannesmann Demag; Creusot-Loire-Uddeholm
Reduction mix bin
(CLU)10 process, shown in Fig. 12.4; Sumitomo
11
top and bottom (STB) blowing process by
Sumitomo Metals; top mixed bottom inert
up / down
(TMBI)12 process used by Allegheny Ludlum
Corporation; VODC13 process tried by Thyssen
Standby
where vacuum is applied to the converter; and
14
AOD/VCR process developed by Daido,
shown in Fig. 12.5.
Vacuum lid
The development work to make stainless steels
using conventional BOF converters had begun
in the late 1950s and early 1960s. By the mid1960s, some steelmakers were using existing
BOF converters for a partial decarburization
followed by decarburization in a ladle under
vacuum to make the low carbon stainless
steels. These processes are known as triplex
processes because three process units, such as
electric arc furnace, a converter for pre-blowing, and a vacuum decarburization unit for
final refining, are involved. The steels undergo
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
717
treatment for final decarburization, final trimming, homogenization and flotation of inclusions
before the ladle is taken to the teeming operation. In almost all of these triplex processes, vacuum
processing steels in the teeming ladle is the final step before casting. The vacuum oxygen decarburization (VOD) process was developed by Thyssen in West Germany.15 The other processes using
vacuum include the use of RH-OB for making stainless steels at Nippon Steel Corporation16 and the
use of an SS-VOD process17 by Kawasaki Steel Corporation. These processes are shown in Fig. 12.6.
With all these developments over several decades, now there are many different processes to make
stainless steels. The available processes can be divided into three groups: the converter processes,
converter with vacuum processes, and vacuum processes. Table 12.1 shows the variety of
processes.
Table 12.1 Different Process Routes for Making Stainless Steels
Process
AOD
KCB-S
K-BOP/K-OBM-S
MRP, ASM
CLU
AOD-VCR (vacuum)
VOD (vacuum)
Tuyere Location
Side
Side
Bottom or Side
Bottom
Bottom
Side
Bottom (bubbler)
Bottom Gases
O2, N2, Ar, Air, CO2
O2, N2, Ar
O2, N2, Ar, Hydrocarbons
O2, N2, Ar
O2, Steam, N2, Ar
O2, N, Ar2, N2, Ar
Ar, O2
Top Gases
O2, N2, Ar
O2, N2, Ar
O2, N2, Ar
O2, N2, Ar
O2 lance
O2 lance
to
vacuum
Ar
Ar
Oxygen
blowing
lance
VOD
CO CO
Tank VOD
or SSVOD
Post-combustion
CO(g) + 1/2O2 = CO2 + Q
[C] + 1/2O2 = CO(g)
Ladle
RH-OB
718
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A worldwide survey of the steel companies using one of these processes to make stainless steels is
given in Table 12.2. Only the companies with process vessels larger than 20 tons are considered. A
number in parentheses indicates the number of similar converter vessels currently operated by the
company. A slash indicates the company also uses another process. Companies that have known
vacuum processing capability are noted. This list is by no means comprehensive.
Table 12.2 Survey of Steel Companies and Processes Used
Company
Converter
AOD
AOD
(2) AOD
AOD/MRP-L
(2) AOD
AOD
MRP
(2) AOD
AOD
AOD
AOD
(3) AOD/CLU
AOD
(3) AOD
KCB-S
LD
AOD
AOD/CLU
AOD
(2) AOD/AOD-VCR
(2) AOD
AOD
ASM
CLU
AOD
AOD
AOD
ASM
ASM
AOD
(2) ASM
AOD
K-BOP
ASM
(5) AOD
ASM
AOD
AOD
CLU
AOD
ASM
AOD
K-OBM-S
ASM
Vacuum
VOD
VOD
(2) VOD
VOD
VOD
VOD
VOD
VOD
VOD
VOD
VOD
continued
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719
Converter
Vacuum
(2) AOD
AOD
AOD
LD
OTB
AOD
(2) AOD
(3) AOD
AOD
ASM
AOD/K-OBM-S
ASM
AOD
AOD
AOD
AOD
(2) VOD
VOD
VOD
VOD
VOD
MRP
AOD
(2) AOD
AOD
(3) AOD
AOD
AOD/K-OBM-S
ASM
MRP-L
MRP-L
AOD
VOD
VOD
VOD
VOD
In the following sections, the various processes for making stainless steels are discussed. First,
there is a brief discussion of the general principles of refining stainless steels, followed by an
examination of process routes. Then the melting of scrap and raw materials is described. Melting
methods are common to all the duplex and triplex routes for making stainless steels. Most steel
plants use electric arc furnaces for melting scrap and raw materials. Alternative technologies such
as a direct current furnace, a plasma furnace or a similar melting unit can serve the same purpose.
The balance of the chapter is devoted to a discussion of refining methods.
(12.2.1)
(12.2.2)
Decarburization occurs on the surface of rising bubbles that form from either the inert gas that is
injected or on the suface of chromium oxide particles that are being reduced and generating CO.
The decarburization of stainless steel involves techniques to minimize chromium oxidation. There
are three basic techniques: temperature, dilution, and vacuum.
720
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The temperature technique was used by electric arc furnace stainless steelmaking before the development of duplex methods. As shown in Chapter 2, Section 2.9.1, as the temperature increases, the
equilibrium carbon content at a particular chromium content decreases. As discussed above, however, this leads to operational difficulties and high costs.
The dilution technique is that used by the AOD and all converter processes. The injection of inert
gas (argon or nitrogen) lowers the partial pressure of CO in the bath, thus allowing higher chromium
contents to be in equilibrium with lower carbon contents, as shown in Chapter 2, Section 2.9.1.
Applying a vacuum to the metal bath also removes CO, allowing high chromium contents to be in
equilibrium with low carbon contents. It is especially effective when the carbon content is low.
Careful manipulation of the slag, as it participates in the reaction, is important. Any chromium
oxide not reduced by carbon ends up in the slag, which can form a complex spinel. Subsequent processing (called reduction) is required to recover oxidized elements such as chromium, iron, manganese, etc. The effectiveness of the reduction step is dependent on many factors including slag
basicity and composition, temperature, mixing conditions in the vessel and solid addition dissolution kinetics.20 Chapter 2, Section 2.9.3 describes these reactions in more detail.
Scrap
FeCrHC
Ni
O2
N2 / Ar
O2, N2, Ar
LPG
Duplex route
Ar
Triplex route
Ar
Fig. 12.7 Comparison of duplex and triplex process route in stainless steelmaking.
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721
melting is followed by refining in a converter, tends to be flexible with respect to raw material
selection. Triplex refining, where electric arc furnace melting and converter refining is followed by
refining with a vacuum system, is often desirable when the final product has very low carbon and
nitrogen specifications.21 Triplex refining tends to have overall cycle times longer than duplex
refining because there is an extra transfer from refining converter to vacuum unit. It also tends to
have slightly higher refractory costs because there are two vessels performing decarburization.
Raw material availability affects the choice of process route. For example, high argon costs shift
the economics of stainless production away from dilution type processes in favor of vacuum
processes. A lack of scrap forces the use of more high carbon ferrochrome, increasing the carbon
load in the charge. In such a case, process routes that have high decarburization rates would be
favored. Lack of scrap, which can be used for cooling the bath, also can favor processes that are
not thermally efficient, as there is no economical addition for cooling the bath. Where scrap and
ferroalloys are expensive or unavailable, process routes have been developed that use chromium
ore and blast furnace or similar hot metal.22, 23 These processes typically incorporate a smelting
unit, often a converter, to reduce the ore, followed by decarburization in another converter, possibly followed by vacuum processing.
The desired product mix affects the choice of process. High production levels of ultra low carbon
and nitrogen stainless steels tend to favor vacuum processes to avoid high argon consumption. For
typical levels of carbon and nitrogen in stainless steels, the processing cost are usually lower for
the converter processes than vacuum or triplex processes.
Downstream processing considerations also will affect the choice of process. Sequence continuous
casting requires a stainless steel refining route that will provide feed metal at the proper temperature, composition and time to sequence cast.
Availability of ladle furnaces and ladle stations can shift some of the non-decarburization time
from the refining vessel to the ladle furnace or station. Some high productivity shops tap the heat
out of the converter just after the reduction stage. The final additions are made to the ladle. This
frees up the refining vessel for the next heat.
If existing melting capacity is insufficient for desired production levels, the refining process may
need to melt large amounts of cold material. This would favor processes that are thermally efficient
or ones that can generate heat for melting. If melting is primarily by induction furnaces, raw material choices may be limited. Blast furnace or hot metal availability would also influence the type
of refining process. Available vacuum or baghouse capacity may influence the choice between vacuum or dilution methods. Crane capacity may limit vessel size. Crane traffic and shop layout will
affect process flow. Existing ladle cars can help or hinder material movement. An existing continuous caster also would affect process choice.
Cost of capital always affects process choices. Systems for making alloy additions can be very expensive. Baghouse and vacuum capacity is also expensive. There is often a balance between capital and
operational cost. The process with the lower operating cost sometimes has the highest capital cost.
In some recent installations, capital spending considerations have eclipsed those of all other factors, including flexibility and operating costs, in the selection of process route. For major turnkey
installations, which may include steel melting, refining, casting, hot and cold rolling, anneal and
pickle lines, as well as the associated technology, the choice of equipment suppliers is limited to
three or four large firms. Each of these suppliers aggressively promotes its own secondary steelmaking process as superior relative to operating costs, quality, productivity, etc. However, several
of these suppliers will manufacture and install a version of any other type of secondary steelmaking, if the customer insists. Depending on geographical location, order backlogs, previous equipment sales, manpower availability, etc., any one of these suppliers may be in a better position to
manufacture and install equipment at a substantially lower price than the others.
For maximum flexibility, a shop should have a process flow that can incorporate a duplex or triplex
route. This offers the most flexibility in raw materials, production capability, and process flow. In
722
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this case, only products that require vacuum refining for economic and/or quality reasons will use
a triplex route.
Carbon
Chromium
Silicon
0.10
0.13
0.045
0.01
2
7.4
7.7
0.055
69
70.7
67.8
69
55
68.7
69.2
37
0.9
0.9
0.63
0.28
0.1
0.85
0.17
40
Nitrogen
Manganese
0.01
0.2
0.45
0.15
0.22
0.16
0.27
Nickel is present in significant amounts in the AISI 200 and 300 series stainless steels. In addition
to austenitic stainless steel scrap, nickel is available as electrolytic nickel, nickel powder, nickel
oxide, briquetted nickel and ferronickel. Typical analyses of nickel containing raw materials are
given in Table 12.4.
Table 12.4 Raw Materials Used to Supply Nickel Units
Nickel Additives
Carbon
Nickel
Silicon
Cobalt
Sulfur
Chromium
Copper
Nickel Briquettes
Low Carbon Nickel Shot
High Carbon Nickel Shot
Nickel Pig
Nickel Copper Shot
Nickel Oxide Sinter
0.01
1.64
0.07
0.3
99.9
50
28
39
51
75
0.02
1.4
0.4
0.1
0.78
0.6
0.7
0.007
0.06
0.015
0.007
0.7
0.15
1.2
26.5
Manganese is present in significant amounts in the AISI 200 series of alloys. Sources of manganese
are given in Table 12.5.
Table 12.5 Raw Materials Used to Supply Manganese Units
Manganese Additives
Carbon
Manganese
Silicon
Electrolytic Manganese
Ferromanganese
Manganese-Silicon
7.1
0.07
99.99
79
61
0.05
31
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723
Silicon is used in all the stainless steel making processes to chemically reduce the chromium which
is present in the slag at the end of the decarburization period. For this purpose, silicon is added in
the reduction mix as ferrosilicon or ferrochromiumsilicon. Additional silicon would be needed to
meet any silicon specification on many of these stainless steels. The most common raw materials
used to supply the silicon are its ferroalloys which contain nominally either 50% silicon or 75%
silicon.
Molybdenum is added to some of the stainless steel grades. The materials which can be used to add
molybdenum include molybdenum oxide in powder or briquette form and ferromolybdenum.
Aluminum is a common deoxidant and high purity aluminum pig or bar is added for this purpose.
Titanium is a very frequent addition to many stainless steel grades for the purpose of stabilization
(see Chapter 11). The most commonly used alloys of titanium are 70%Ti30%Fe and
90%Ti4%V5%%Al alloy. The other elements which are generally added in the ladle include carbon, sulfur, nitrogen, niobium (columbium), tungsten and copper. Selenium and tantalum are
added to a very limited number of grades.
In stainless steelmaking, most of the cost of the final product is due to raw materials. Over more
than the past two decades, computer programs, most of which use linear programming techniques,
have been developed and used to utilize the raw materials in such a way that the total raw material
cost of production is minimized.
12.5 Melting
For the electric arc furnace, typical charges are scrap and ferroalloys. As there is further refining,
least cost charges incorporate high carbon ferroalloys for chromium and manganese units.
Usually, the least cost source of material is used; for scrap this may consist of oily turnings and
furnace skulls.
Sometimes, hot metal from the blast furnace or other iron source is available. In this case, the
electric arc furnace can be used to melt only ferroalloys with the resulting melt then mixed with
the molten iron in a converter process for refining.22 The electric arc furnace can also be bypassed
altogether.
When hot metal is the source and stainless scrap or ferroalloys are unavailable or too expensive,
then chromium, manganese and nickel ores can be used as sources of material.23, 24
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For a 300 series stainless steel, a typical melt-in mixture might consist of: 50% 300 series scrap
(18%Cr, 8%Ni, 1%Mn); 30% carbon steel scrap;14% high carbon ferrochrome (7%C, 65%Cr); 4%
nickel (commercial purity); and 1% high carbon ferromanganese (7%C, 65%Mn).
At melt-in, this mixture would yield about 18%Cr, 8%Ni, 1%Mn and 1%C.
In the early stages of melting, some shops will use burners and oxygen lancing. The added energy
input increases the melt-in rate in the early stages of melting. After the second bucket however,
burner and oxygen use is limited to avoid chromium oxidation. At tap, ferrosilicon is often added
to recover oxidized chromium from the slag.
725
Argon
Nitrogen
Oxygen
Lime
Spar
Aluminum
Silicon (reduction)
Brick
Decarburization metallics
Charge to tap time
Total Cr yield
Total Mn yield
Total Metallic yield
*1.8%
Units
Typical
Best
Nm3/ton
Nm3/ton
Nm3/ton
kg/ton
kg/ton
kg/ton
kg/ton
kg/ton
kg/ton
min.
%EAF/AOD
%EAF/AOD
%EAF/AOD
12
911
2532
5060
3
2
89
59
135
5080
9697
88
95
9
9
NA
42
2
1
6
2
NA
40
99.5
95
97
A major modification of the original AOD process involves the use of a top-blowing lance in addition to the side blowing tuyeres. The lance can be used to inject oxygen at desired flow rates to
increase decarburization and/or for post-combustion. The top lance can also be designed for blowing mixed gases such as inert-oxygen gas mixtures. The installation of a lance and introduction of
oxygen in the early stages of decarburization can reduce the time for a heat. The technology can
be used to increase productivity, in tons per hour, of a melt shop.
Another modification of the AOD involves applying vacuum on the converter to reduce the argon
and silicon consumption as well as process time when making low carbon grades. This modification is identified as AOD-VCR and is used by Daido Steel, Japan.
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
helpful in increasing the refractory life. Typical consumptions and conditions 21 for making AISI
304 are given in Table 12.7.
Table 12.7 Consumptions and Conditions for AISI 304
Condition/Addition
Units
Typical Values
Aim carbon
Aim nitrogen
Melt-in carbon
Melt-in silicon
Oxygen
Nitrogen
Argon
Silicon (reduction)
Lime
Dolomite
Fluorspar
%
ppm
%
%
Nm3/ton
Nm3/ton
Nm3/ton
kg/ton
kg/ton
kg/ton
kg/ton
0.033
300
1.77
0.13
29.5
13.2
16.5
11.1
51
20
7.9
727
The decarburization period consists of injecting an oxygen-steam mixture. The process is energy
inefficient as the reaction of steam with the molten steel bath is endothermic. Chromium oxidation
is higher than in the AOD process when decarburization is continued below about 0.18% carbon.
Although the original goal of reducing argon consumption can be met, the increased silicon
requirement for the reduction step does not necessarily lead to overall cost savings. Further, the use
of steam throughout the entire period was found to lead to undesirable hydrogen contents in the
refined steel. Therefore, practices have evolved which use various amounts of steam, argon, and
nitrogen in the process. Consumptions and conditions32 for two grades are given in Table 12.8.
Table 12.8 Consumptions and Conditions for AISI 304 and AISI 409
Condition/Addition
Units
AISI 304
AISI 409
Aim carbon
Aim nitrogen
Melt-in carbon
Melt-in silicon
Oxygen
Nitrogen
Steam
Hydrogen
Argon
Silicon (reduction)
%
ppm
%
%
Nm3/ton
Nm3/ton
Nm3/ton
ppm
Nm3/ton
kg/ton
0.03
350
1.65
0.2
27.7
13.5
10.4
5.9
7.0
15.5
0.01
100
0.96
0.13
22.4
1.7
6.0
3.8
17.1
15.9
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
729
processes are performed in a chamber with a ladle full of metal as opposed to a separate refining
vessel used in the dilution/converter processes.
In mid 1960s, the vacuum decarburization concept was used by Allegheny Ludlum Steel
Corporation to develop the Allegheny vacuum refining process. It was used to make the regular
grades of stainless steels and lowered the consumption of low carbon ferrochrome associated with
the oxidation-reduction practice used in the electric arc furnace. This process became non-competitive with the introduction of the AOD process. In late 1970s, Allegheny Ludlum built a plant
with an AOD reactor and discontinued the use of the AVR process.
Early duplex processes where vacuum processing was used as the second step were too slow and
had very limited flexibility with respect to raw materials that could be used. The vacuum processes
could not keep up with the improving productivity of electric arc melting furnaces and the operating costs were very high. Hence, later developments focused on the use of converters to decarburize the molten metal from electric arc furnaces as a second stage followed by vacuum degassing
for the finishing stage. Such processes are known as triplex processes for making stainless steels
as they use three processes to achieve the desired finished chemistry.
Nippon Steel Corporation introduced the RH-OB process for making of stainless steels in the
Muroran Works.41 Hot metal from a blast furnace was fed to a BOF converter where the metal was
alloyed with chromium and blown down to a 0.50.6% carbon level. The final decarburization was
conducted using the RH-OB process. Nippon Steel converted an existing RH degasser, which was
used for carbon steels, so that oxygen could be injected under vacuum.
Edelstahlwerk Witten (now Thyssen) in Germany developed the vacuum oxygen decarburization
(VOD) process in the mid-1960s. In the early stages of its development, VOD was used to decarburize molten alloy from the electric arc furnace. Later, preliminary decarburization was done in a
BOF and the EAF-BOF-VOD triplex process became more productive. In early 1970s, Kawasaki
Steel Corporation modified the VOD process using multiple porous plug bubblers in the ladle.
They called this the SS-VOD (strong stirring VOD) process.42 In 1988, ALZ in Belgium modified
the facilities to make stainless steels by a triplex process consisting of electric arc furnace melting,
metal refining process-lance (MRP-L) converter, and vacuum oxygen decarburization (VOD)
process.43
The major advantages of the vacuum processes include low consumption of argon and low oxidation of chromium during the final decarburization to low carbon levels. The latter leads to less consumption of reduction elements for recovering chromium from slag. The teeming of steel from the
ladle used in the vacuum processes eliminates the pickup of nitrogen and oxygen from air that is
associated with tapping of the converters. The SS-VOD process, because of the strong stirring
achieved using multiple bubblers in the ladle, further enhanced the ability to produce even lower
levels of carbon, nitrogen and hydrogen at higher chromium levels.
A major disadvantage of VOD processing is that it is less flexible than an AOD or other converter
process with respect to raw materials usage. Typical additions to the VOD are around 48% of tap
weight. Typical vacuum treatment times are 50 to 70 minutes with start carbon contents of 0.3%,
compared with 40 to 60 minutes with a converter starting at 1.5 to 2.5%C. This added time makes
it difficult to sequence continuous casting of heats.
Many steelmakers have also realized that vacuum processes often have high operating costs and
cannot compete with the ease of operating a converter process at atmospheric pressure. However,
the vacuum processes, especially the SS-VOD process, have the unique ability of achieving lower
carbon and nitrogen levels in stainless steels which cannot be easily achieved by the AOD process
or other converter processes.
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
Hot metal
dephosphorization
Direct reduction
of chromium ore
and scrap melting
SR-KCB
O2
Ar
Prevention of
chromium
oxidation by
using mixed gas
Lower cost
refining for high
grade steel
DC-KCB
VOD
processes commercially. In particular, Kawasaki Steel Corporation (KSC) has developed a process
which smelts chromite ore (FeCr2O4 plus other oxides). Stainless steel is produced with two 160
ton converters, without any EAF operation, but using dephosphorized hot metal, chromite ore and
ferroalloys as the major charge materials. An outline of the KSC process is shown in Fig. 12.8. The
hot metal is desulfurized and then fed into a K-BOP/K-OBM vessel (SR-KCB) which is described
in Chapter 9. Chromite pellets, which are partially prereduced up to 60% chromium content by
rotary kiln, are charged to the first reactor. Coke is also charged and serves as a heat source in the
reactor. The charging rate of ore and coke and the oxygen blow rate are controlled to achieve suitable temperature for the melt.44, 45
The steel melt, which now contains about 1116% Cr and 56% C is charged to the second KBOP/K-OBM vessel. Primary decarburization (DC-KCB) is carried out using oxygen, argon and
nitrogen gases in this vessel. Top and bottom oxygen blowing is used to lower the carbon content
of the melt to about the 1% level. This is followed by mixed gas blowing only from the bottom.
This is called the DC-KCB process and is similar to a modern AOD operation. The process reduces
the carbon to about 0.15%. Final decarburization and reduction is carried out in a VOD. The
process uses less amount of scraps than the EAF-AOD process route. However, it requires liquid
hot metal from a blast furnace and more process steps and more capital investment than the EAFAOD route.
NKK Corp. has developed and commercialized a similar process which also smelts both chromite
and nickel ore.46 After hot metal dephosphorization, the metal is transferred to a smelting furnace
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
731
and nickel ore is smelted. As a nickel ore typically contains 13% nickel, a considerable amount of
ore is added and the slag must be removed several times to achieve the desired nickel level. After
reaching the required nickel content, chromite or chromium ore is smelted. The smelting takes about
six hours; four for nickel and two for chromium. This is followed by the decarburization period.
Similar to the KSC process, the NKK process uses less scrap and only a small amount of nickel
metal and ferrochrome. However, the process requires hot metal and a very long process time.
These direct stainless steelmaking processes require less scrap and ferroalloys and may be considered when the stainless scrap and ferroalloys are not readily available in sufficient quantities.
However, chromium and nickel ores are needed and can be used in an integrated steel plant where
the hot metal is available. The processes are more capital intensive than the other processes.
Therefore, their implementation in other plants and locations is likely to be limited.
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
For vessels that tap into a ladle held by a crane, a sliced cone top section is often used. The slice
portion allows the crane to come close to the vessel mouth. Fig. 12.2 shows an AOD vessel with a
sliced cone top section. Vessels that tap into a ladle car usually have a BOF-type concentric cone
top section.
12.9.2 Refractories
High temperatures at the tuyere tip and high bath agitation place great demands on the vessel
refractory.48 While typical BOF refractory campaigns are months or years long, stainless converter
campaigns are several days or weeks long. Refractory costs are a significant fraction of total operating costs.
There are two basic choices of refractory type, magnesite-chromite, and dolomite. The choice of
refractory is dependent on the vessel operation pattern, final product specifications, and economics.
Magnesite-chromite refractories have high wear resistance but have a higher unit cost than
dolomitic refractories. Chromium pickup from the brick is possible. Magnesite-chromite bricks are
simultaneously acidic and basic and strict slag compositions must be maintained to prevent rapid
wear.49,50,51
Dolomitic refractories are usually less costly than magnesite-chromite refractories and chromium
pickup is not a factor. Desulfurization to very low levels is generally easier in dolomitic refractories because very basic slags can be used without detrimental effects to the brick.52 Most major
stainless producers in the United States and Europe use dolomitic refractories in the converter.
Vessels are typically zoned by thickness and brick quality to maximize lining life and minimize
costs. High wear areas of the vessel, usually the tuyere wall, slag line, and transfer pad (where the
metal stream strikes the vessel during transfer) are zoned thicker and with higher quality refractory
than other parts of the vessel.
For more analysis of stainless steelmaking refractories, see Section 4.4.
733
The amount of oxygen that reacts with the bath can range from 30 to 100% of the oxygen blown.
This amount depends on lance height, nozzle design and gas pressure used.
There are two basic lance types, sonic/subsonic and supersonic. Sonic/subsonic lances consist of
straight pipes, while supersonic lances use converging/diverging (Laval) nozzles. Supersonic
lances are always water cooled. Sonic/subsonic lances might be water cooled depending on lance
operating position. Smaller sonic/subsonic lances often are not water cooled. Many sonic/subsonic
lances are simple pipes with nickel or calorized tips to increase heat resistance.
A water-cooled lance is typically positioned one to four metres from the bath surface. Non-watercooled lances are positioned close to the vessel mouth.
Supersonic lances are used for high oxygen input rates where post-combustion is not required. A
great majority of the oxygen from a supersonic lance will react with the bath.54 As in BOF operation, the lance can have post-combustion ports.
With sonic lances, some of the oxygen will not react with the bath; some post-combustion is
inevitable.55 Heat balances indicate that 75 to 90% of available energy from post-combustion is
transferred to the molten bath. The simplicity of a non-water-cooled sonic lance makes it attractive
to smaller shops.
Inert gases are sometimes injected with the oxygen from the top lance to extend the period the topblown gases are used. Argon top blowing can reduce air infiltration into the vessel and improve carbon removal efficiency in the late stages of the decarburization blow. This is especially true for vessels
where high rate bottom argon blowing causes excessive splashing, vibration, or refractory wear.
A recent development in top lance technology is the development of top heating. An oxy-fuel
burner in the top of the vessel provides heat to the vessel during operation.56 This results in benefits similar to post-combustion.
12.9.5 Gases
Pure argon, oxygen, and nitrogen are used by virtually all shops. In rare cases, nitrogen is not used
because the product mix or operation pattern does not warrant the extra cost of supplying nitrogen.
Some other gases used are crude argon, high-pressure air, non-cryogenic nitrogen and oxygen,
hydrocarbons, and carbon dioxide. These other gas choices depend on operational pattern, relative
cost of supply and product mix.
Crude argon contains 9597% argon, 13% oxygen, and 0.52% nitrogen. It can be used in the
middle to late stages of decarburization and reduction, depending on final product specifications.
The choice of using crude argon is dependent on availability, relative cost to pure argon, and product specifications.
High-pressure air can be used to partially replace nitrogen, but the capital and maintenance cost of
compressors and associated equipment limit this option to larger melt shops. Non-cryogenic nitrogen and oxygen sources also require some compression for use in refining processes, and the
choice of this supply method again depends on pure versus non-cryogenic prices, duty cycle, power
costs and production rates compared to pure gases.57
Carbon dioxide and hydrocarbons can be used as process gases down to certain carbon levels. In
stainless production, increased chromium oxidation below 0.3%C by carbon dioxide58 or hydrogen
and carbon pickup from hydrocarbons limits the use of these gases. The replacement of nitrogen
by these gases depends on the relative cost of the gases. Low nitrogen specification grades of stainless steel, which typically are made using only argon as an inert gas, can use carbon dioxide as a
replacement for argon in the early stages of decarburization.
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
Some vessels are designed to rotate 360. Side-blown vessels generally have replaceable shells.
With removable vessels, crane access and capacity are considerations in the placement and size of
the operating unit.
The trunnion bearings and drive must be designed to handle the vibration and rocking motion of
the converter during processing.
12.10.1 Decarburization
After the molten charge is in the vessel, an oxygen-inert gas (argon, nitrogen, or carbon dioxide)
mixture is injected into the vessel. The initial oxygen to inert ratio generally varies in the range
of 5:1 to 3:1 and is lowered with the progress of decarburization. The major benefit associated
with the dilution process comes into play when the oxygen to inert gas ratio is 1:1 and then furCopyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
735
ther reduced to 1:3 or lower. Oxidation of carbon continues, but oxidation of chromium is limited.
The latter is due to the very low oxygen potential of the gas mixture, which minimizes chromium
oxidation.
For a 300 series stainless, a typical stepped blow would be 1.5 Nm3/min/ton oxygen mixed with
0.5 Nm3/min/ton inert gas from the start carbon content to 0.35%C, then 0.5 Nm3/min/ton oxygen
mixed with 0.5 Nm3/min/ton inert gas to 0.15%C, followed by 0.25 Nm3/min/ton oxygen mixed
with 0.75 Nm3/min/ton inert gas to 0.05%C; and then 100% argon to final specification.
More recent blow programs consist of using a starting oxygen to inert gas ratio of higher than 3:1
and continuous adjustment of the oxygen to inert gas ratio during the blowing period. Depending
on the aim nitrogen content, nitrogen can be used as the inert gas for a period of the oxygen blow.
Beginning carbon levels in converter processing may range from 0.74.5%C, with a typical range
of 1.02.5%. Typical silicon levels range 0.20.4% before decarburization.
If a top lance is available, it is used during the high oxygen to inert gas periods. Some vessels use
a top lance to add heat. The top heating lance is a modified oxy-fuel burner.
During decarburization, additions are made for obtaining the proper final chemical composition.
These additions usually consist of desired amounts of high carbon ferrochromium, stainless steel
scrap, carbon steel scrap, nickel, iron, high carbon ferromanganese, and molybdenum oxide. These
additions serve to reduce the bath temperature as carbon and chromium oxidation are exothermic.
In general, the bath temperature is controlled to less than 1720C. Total alloy addition weights are
in the range of 530% of tap weight.
Lime or dolomitic limes are usually added just before the oxygen blow to flux the transfer slag and
silicon in the metal. During the oxygen blow, silicon is oxidized before carbon. Lime and dolomitic
lime are sometimes added before the end of the blow to cool the bath and to reduce the volume of
reduction additions. Slag fluxing additions, such as lime, dolomitic lime and spar, are typically in
the range of 37% total bath weight.
It follows that the length of the blow period is determined by the starting carbon and silicon levels
of the hot metal charged to the AOD. Decarburization times range from 20 to 35 minutes in modern converters (start carbon 1.5 to 2.5% and aim carbon 0.04%). Usually, the vessel is turned down
to a horizontal position and a sample of the melt is taken for analyses at a carbon level of about
0.1%. Some high productivity shops can sample without rotating the vessel by using a sub-lance.
The steel sample is analyzed for carbon. The temperature of the steel bath is also measured.
The next step is the reduction step, in which the reduction additions are charged and stirred with
an inert gas for a desired time. The reduction mix consists of silicon alloys, such as ferrosilicon or
chromium-silicon, and/or aluminum, which are added for the reduction of metallic oxides from the
slag and fluxing agents such as limestone, lime, dolomitic lime, and fluorspar. The bath is then
stirred with inert gas, typically for only for five to eight minutes. An example of a reduction mix
is given in Chapter 2, Section 2.9.3.
The formation of a high basicity slag and the reduction of oxygen potential in the metal bath are
good conditions for sulfur removal. For example, with a start sulfur of 0.03%, a reduction treatment of 23 kg aluminum/ton, 23 kg spar/ton, final slag basicity of about 1.7, and temperature of
1700C, finish sulfur contents of 0.0030.005% can be obtained.
If the grade to be produced requires an extra low sulfur level, the bath is deslagged after the reduction step and another basic slag is added. The liquid steel and the fluxes are then mixed to complete the desulfurization reaction. In modern practices a sulfur level of 0.001% or less is easily
achieved with this double slag practice.
Ideally, at this stage of the process, the chemistry of the liquid steel should meet final specifications so that the heat can be tapped. If necessary, additional raw materials may need to be charged
for small chemistry adjustments. Depending on the grade, additional deoxidation or alloying additions maybe needed. Such final additions are stirred in the AOD just before tap or are added in
the tap ladle.
736
Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.
Following tap, the ladle is often stirred for composition homogenization and temperature uniformity along with flotation of inclusions. This is done in a ladle equipped with stirring facilities with
or without the use of a ladle furnace. After the ladle treatment, the steel is ready to be cast.
12.10.2 Refining
The amount of stirring energy from the gas blown through the subsurface tuyeres and the formation of carbon monoxide deep within the metal bath results in the converter processes being among
the most intensely stirred metallurgical reactors. The intimate gasmetal contact and excellent
slagmetal mixing facilitate refining reactions.
Sulfur removal is a slagmetal reaction that occurs during the reduction phase of the process.
Phosphorus, which requires oxidizing conditions, cannot be removed in the converter processing.
Nitrogen control is a gasmetal reaction. Depending on final nitrogen specifications for the stainless grade, the inert gas during the initial stages of decarburization can be nitrogen. After a certain
carbon level is achieved, the nitrogen gas is replaced by argon. Such an approach is practiced by
all steelmakers to reduce argon usage and costs and still achieve a desired nitrogen specification.
After the change from nitrogen to argon, nitrogen is removed from the bath by both evolved carbon monoxide and argon.59,60 Volatile elements with high vapor pressures, such as lead, zinc, and
bismuth, are removed during the decarburization period.61
737
content, inclusion shape control, improved weldability, and decreased dissolved oxygen levels.
Ladle additions of deoxidizing compounds are common. Wire feeding is used to add alloys of titanium, aluminum, calcium, and sulfur to improve alloy recoveries and quality.
Some operators use ladle furnaces to provide additional heat to perform the above operations.
Carbon pickup from the electrode arcs can be minimized by close control of slag thickness, arc
length and stirring rates, even when treating ultra-low carbon grades.
Shops having vacuum refining units would normally use these for the last stage of decarburization
on ultra-low carbon (ULC) and ultra-low nitrogen (ULN) grades or as part of the triplex (EAFConverter-VOD) process.
12.11 Summary
Stainless steels were developed at the beginning of the 20th century. Their unique properties have
led to their use in many different applications. Fundamental research in the thermodynamics and
kinetics led to understanding of the phenomenon associated with chromium oxidation and how to
minimize it. The development of the argon oxygen decarburization (AOD) process revolutionized
stainless steelmaking. This process, based on the dilution principle, allowed steelmakers to use
lower cost raw materials and to shorten the steelmaking times compared to the other processes in
use at that time. This led to lowering the cost of producing stainless steels. This, in turn, led to dramatic increases in the applications for stainless steels. Over the years, other processes have been
developed for making stainless steels. Most of these use vessels or reactors in which gases are
introduced to carry out the necessary decarburization reactions. Some of these processes for making stainless steels utilize decarburization under vacuum.
Of the many specific processes available for stainless steel refining, argon oxygen decarburization
and its converter-based variants are by far the most commercially popular. For maximum flexibility to produce a very wide range of stainless steel grades, a modern melt shop may have a source
of molten metal, a converter that can produce most grades economically (duplex processing) and
a vacuum unit for further processing of extra low carbon and nitrogen grades (triplex processing).
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741